CN113957417A - CVD fluidized deposition device and preparation method of silicon-carbon negative electrode material - Google Patents
CVD fluidized deposition device and preparation method of silicon-carbon negative electrode material Download PDFInfo
- Publication number
- CN113957417A CN113957417A CN202111070124.3A CN202111070124A CN113957417A CN 113957417 A CN113957417 A CN 113957417A CN 202111070124 A CN202111070124 A CN 202111070124A CN 113957417 A CN113957417 A CN 113957417A
- Authority
- CN
- China
- Prior art keywords
- carbon
- conveying mechanism
- gas
- silicon
- reaction cavity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000008021 deposition Effects 0.000 title claims abstract description 67
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007773 negative electrode material Substances 0.000 title claims description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 102
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000007789 gas Substances 0.000 claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 239000010703 silicon Substances 0.000 claims abstract description 37
- 239000012159 carrier gas Substances 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000011084 recovery Methods 0.000 claims abstract description 19
- 238000007599 discharging Methods 0.000 claims abstract 3
- 238000005243 fluidization Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- 239000010405 anode material Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- VJIYRPVGAZXYBD-UHFFFAOYSA-N dibromosilane Chemical compound Br[SiH2]Br VJIYRPVGAZXYBD-UHFFFAOYSA-N 0.000 claims description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 claims description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 2
- IBOKZQNMFSHYNQ-UHFFFAOYSA-N tribromosilane Chemical compound Br[SiH](Br)Br IBOKZQNMFSHYNQ-UHFFFAOYSA-N 0.000 claims description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 55
- 239000010406 cathode material Substances 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000012071 phase Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910021383 artificial graphite Inorganic materials 0.000 description 8
- 239000005543 nano-size silicon particle Substances 0.000 description 6
- 229910021382 natural graphite Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910003676 SiBr4 Inorganic materials 0.000 description 3
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910003818 SiH2Cl2 Inorganic materials 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910003822 SiHCl3 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/442—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using fluidised bed process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/24—Deposition of silicon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4417—Methods specially adapted for coating powder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a CVD fluidized deposition device and a preparation method of a silicon-carbon cathode material, wherein the CVD fluidized deposition device comprises a fluidized bed with a reaction cavity, a heating device for heating the reaction cavity and a collecting hopper for collecting the fluidized deposition material are arranged in the reaction cavity, the fluidized bed is connected with a carbon-based material conveying mechanism for conveying the carbon-based material into the reaction cavity, a gas-phase material conveying mechanism for conveying silicon source gas and reducing gas into the reaction cavity, a carrier gas conveying mechanism for inputting carrier gas into the reaction cavity and a negative pressure recovery assembly for recovering excess materials, a guide plate for dividing the reaction cavity into a fluidized cavity and a discharging cavity is arranged in the reaction cavity, the carbon-based material conveying mechanism, the gas-phase material conveying mechanism and the negative pressure recovery assembly are communicated with the fluidized cavity, and the carrier gas conveying mechanism is communicated with the discharging cavity. The CVD fluidized deposition device has the advantages of good coating, reliable work, high automation degree and high production efficiency.
Description
Technical Field
The invention relates to the technical field of chemical vapor deposition equipment, in particular to a CVD fluidized deposition device and a preparation method of a silicon-carbon negative electrode material.
Background
Due to the advantages of high theoretical capacity (4200mAh/g), low discharge platform, abundant reserves and the like, the silicon negative electrode material becomes a new-generation negative electrode material which is most likely to replace the traditional graphite negative electrode material at present.
Silicon deposition is common in solar synthesis of polycrystalline or amorphous silicon by introducing Silane (SiH)4) Or (SiHCl)3) Silicon source is equalled, silicon is deposited on the surface of the silicon rod or the seed crystal grain and grows into a large shapeA silicon pillar or a silicon ingot. The reaction achieves the deposition effect by controlling the temperature, the atmosphere concentration and the pressure difference in the bell jar furnace, and realizes the deposition of the silicon rod with the silicon purity of more than 99.999 percent.
At present, the mainstream silicon negative electrode material synthesis scheme is relatively complex, and patent CN107785560A discloses a method for preparing a silicon-carbon negative electrode material by kneading and pressing, wherein the synthesis process comprises compounding carbon such as silicon and graphite, coating amorphous carbon such as asphalt, crushing, sieving, press-forming and the like; the synthesis process is complex, and although some problems in silicon carbon application can be solved to a certain extent, the process is complex, the equipment cost is high, and the preparation of nano silicon has an obvious capacity bottleneck.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a CVD fluidized deposition device which can realize better coating, is reliable in work, high in automation degree, high in production efficiency, simple and compact in structure and low in cost and a preparation method of a silicon-carbon negative electrode material.
In order to solve the technical problems, the invention adopts the following technical scheme:
the utility model provides a CVD fluidization deposition apparatus, is including the fluidized bed that has the reaction chamber, install the heating device who is used for heating the reaction chamber and be used for collecting the collection hopper that fluidizes the deposition material in the reaction chamber, the fluidized bed is connected with and is used for carrying carbon-based material conveying mechanism of carbon-based material in the reaction chamber, is used for carrying silicon source gas and gaseous material conveying mechanism of transport and is used for retrieving the negative pressure recovery subassembly in the reaction chamber to the reaction chamber, be equipped with in the reaction chamber and separate the reaction chamber for fluidization chamber and the guide plate in the play material chamber, carbon-based material conveying mechanism, gaseous material conveying mechanism and negative pressure recovery subassembly all with fluidization chamber intercommunication, carrier gas conveying mechanism with ejection of compact chamber intercommunication.
In the CVD fluidized deposition device, preferably, the fluidized chamber includes a straight cylinder section and an expanding section connected to the upper end of the straight cylinder section, the inner diameter of the expanding section gradually increases from bottom to top, a splitter plate is arranged in the expanding section, the filtering splitter plate is a conical filter plate with an upward vertex, the negative pressure recovery assembly is communicated with a space above the splitter plate, and the carbon-based material conveying mechanism and the gas-phase material conveying mechanism are both communicated with the straight cylinder section. Above-mentioned CVD fluidization deposition apparatus, it is preferred, collect the hopper including the collecting chamber and with the discharge gate that the collecting chamber communicates, the collecting chamber has the direction inclined plane of the fluidization deposition material direction discharge gate in with the collecting chamber, be equipped with on the discharge gate and be used for opening and close the valve of discharge gate.
In the CVD fluidized deposition apparatus, preferably, a discharge port of the collecting hopper is provided with a condenser and a cyclone separator.
In the CVD fluidized deposition apparatus, preferably, the carbon-based material conveying mechanism is a screw feeder, a peristaltic pump or a pneumatic conveyor.
In the CVD fluidized deposition apparatus, preferably, the deflector is a second-stage hole arrangement plate, a dispersion plate, or a molecular sieve type deflector.
Foretell CVD fluidization deposition apparatus, it is preferred, heating device is including installing the tube-shape hot plate in the fluidization intracavity, the tube-shape hot plate is laminated with the inside wall of circular reaction chamber, the bottom of tube-shape hot plate is equipped with the first section of dodging, the first thickness of dodging the section reduces from top to bottom gradually, the top of tube-shape hot plate is equipped with the second and dodges the section, the second dodges the thickness of section and reduces by supreme lower gradually.
As a general technical concept, the present invention also provides a method for preparing a silicon-carbon negative electrode material, which is prepared by using the CVD fluidized deposition apparatus, and comprises the following steps:
s1: inputting carrier gas into the reaction cavity through the carrier gas conveying mechanism to enable the pressure in the reaction cavity to reach a preset pressure, inputting the carbon-based material into the reaction cavity through the carbon-based material conveying mechanism, and adjusting the guide plate to enable the carbon-based material to generate fluidization;
s2: starting a heating device to heat the reaction cavity, so that the temperature in the reaction cavity is raised to a preset reaction temperature;
s3: inputting silicon source gas and reducing gas in a preset proportion into a reaction chamber through a gas-phase material conveying mechanism, and carrying out CVD fluidized deposition on the silicon source gas and the carbon-based material in the reaction chamber to form a fluidized deposition material;
s4: stopping inputting silicon source gas into the reaction cavity after preset time, starting the negative pressure recovery assembly to extract unreacted carbon-based materials, and continuously inputting carrier gas until the temperature of the reaction cavity is reduced to room temperature;
s5: and collecting the silicon-carbon negative electrode material from the collecting hopper.
In the above preparation method of the silicon-carbon negative electrode material, preferably, the silicon source gas is one or a combination of two or more of silane, disilane, dichlorosilane, trichlorosilane, tetrachlorosilane, dibromosilane, tribromosilane and tetrabromosilane.
In the preparation method of the silicon-carbon negative electrode material, preferably, the carbon-based material is one or a combination of more than two of carbon nanotubes, graphene oxide, natural graphite, artificial graphite and carbon microspheres.
In the above preparation method of the silicon-carbon negative electrode material, preferably, the carrier gas input into the reaction chamber by the carrier gas conveying mechanism is nitrogen, argon or helium.
In the preparation method of the silicon-carbon anode material, preferably, the preset reaction temperature is 500-1500 ℃.
In the above preparation method of the silicon-carbon anode material, preferably, the preset pressure is 0.01 to 100 bar.
In the above preparation method of the silicon-carbon negative electrode material, preferably, the reducing gas is hydrogen, and the preset ratio is that the reducing gas is calculated by a molar ratio of: a silicon source gas (2-10): 1; or the reducing gas is nitrogen, and the preset proportion is that the reducing gas is calculated according to the molar ratio: a silicon source gas (1-20): 1.
compared with the prior art, the invention has the advantages that:
when the CVD fluidized deposition device is used, the carbon-based material is conveyed into the reaction cavity through the carbon-based material conveying mechanism, carrier gas is conveyed into the reaction cavity through the carrier gas conveying mechanism to fluidize the carbon-based material in the reaction cavity, silicon source gas and reducing gas are conveyed into the reaction cavity through the gas-phase material conveying mechanism, the silicon source gas and the fluidized carbon-based material are subjected to CVD fluidized deposition in the reaction cavity, silicon is deposited on the surface of the carbon-based material, and good coating is achieved. The silicon-carbon cathode material prepared by the CVD fluidized deposition device has the advantages of uniform structure, high purity, good dispersibility and strong coating binding force. In addition, the device prepares the carbon-silicon cathode material by carrying out fluidized deposition on the silicon source gas and the carbon-based material, the preparation process is not influenced by the bottleneck of nano-silicon productivity, and the production efficiency is high. The CVD fluidized deposition device conveys reactants to the reaction cavity through the carbon-based material conveying mechanism and the gas-phase material conveying mechanism, is reliable in work, high in automation degree, capable of realizing continuous production and high in production efficiency. The CVD fluidized deposition device also has the advantages of simple and compact structure and low cost.
The silicon-carbon cathode material prepared by the preparation method of the silicon-carbon cathode material has the advantages of uniform structure, high purity, good dispersibility, strong coating binding force, no influence from the bottleneck of nano-silicon productivity and high production efficiency.
Drawings
FIG. 1 is a schematic structural view of a CVD fluidized deposition apparatus.
Fig. 2 is an SEM image of the silicon carbon negative electrode material prepared in example 3.
Illustration of the drawings:
1. a reaction chamber; 11. a fluidization chamber; 12. a discharge cavity; 2. a fluidized bed; 21. a diameter expanding section; 3. heating plates; 31. a first avoidance segment; 32. a second avoidance segment; 4. a carbon-based material conveying mechanism; 5. a gas-phase material conveying mechanism; 6. a carrier gas conveying mechanism; 7. a collecting hopper; 71. a material collecting cavity; 711. a guide inclined plane; 72. a discharge port; 73. a valve; 8. a baffle; 9. a negative pressure recovery assembly; 10. a splitter plate.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1:
as shown in FIG. 1, the CVD fluidized deposition apparatus of the present embodiment comprises a fluidized bed 2 having a reaction chamber 1, wherein a heating device for heating the reaction chamber 1 and a collection hopper 7 for collecting a fluidized deposition material are installed in the reaction chamber 1, and the collection hopper 7 is installed in the reaction chamber 1. The fluidized bed 2 is connected with a carbon-based material conveying mechanism 4, a gas-phase material conveying mechanism 5, a carrier gas conveying mechanism 6 and a negative pressure recovery assembly 9. The carbon-based material conveying mechanism 4 is used for conveying the carbon-based material into the reaction chamber 1. The gas-phase material transfer mechanism 5 is used for transferring the silicon source gas and the reducing gas into the reaction chamber 1. The carrier gas delivery mechanism 6 is used for inputting carrier gas into the reaction chamber 1 to fluidize the carbon-based material in the reaction chamber 1. The negative pressure recovery assembly 9 is used for excess materials. A guide plate 8 is arranged in the reaction cavity 1, the guide plate 8 divides the reaction cavity 1 into a fluidization cavity 11 and a discharge cavity 12, the carbon-based material conveying mechanism 4, the gas-phase material conveying mechanism 5 and the negative pressure recovery assembly 9 are communicated with the fluidization cavity 11, and the carrier gas conveying mechanism 6 is communicated with the discharge cavity 12. When the CVD fluidized deposition device is used, the carbon-based material is conveyed into the reaction cavity 1 through the carbon-based material conveying mechanism 4, carrier gas is input into the reaction cavity 1 through the carrier gas conveying mechanism 6 to fluidize the carbon-based material in the reaction cavity 1, silicon source gas and reducing gas are conveyed into the reaction cavity 1 through the gas-phase material conveying mechanism 5, the silicon source gas and the fluidized carbon-based material are subjected to CVD fluidized deposition in the reaction cavity 1, silicon is deposited on the surface of the carbon-based material, and good coating is achieved. The silicon-carbon cathode material prepared by the CVD fluidized deposition device has the advantages of uniform structure, high purity, good dispersibility and strong coating binding force. In addition, the device prepares the carbon-silicon cathode material by carrying out fluidized deposition on the silicon source gas and the carbon-based material, the preparation process is not influenced by the bottleneck of nano-silicon productivity, and the production efficiency is high. The CVD fluidized deposition device conveys reactants to the reaction cavity 1 through the carbon-based material conveying mechanism 4 and the gas-phase material conveying mechanism 5, the operation is reliable, the automation degree is high, the continuous production can be realized, and the production efficiency is high. The CVD fluidized deposition device also has the advantages of simple and compact structure and low cost.
In this embodiment, heating device is including installing tube-shape hot plate 3 in fluidization chamber 11, and tube-shape hot plate 3 and the laminating of the inside wall of circular reaction chamber 1, and the bottom of tube-shape hot plate 3 is equipped with first section 31 of dodging, and the first thickness of dodging section 31 reduces gradually from top to bottom, and the top of tube-shape hot plate 3 is equipped with the second and dodges section 32, and the second dodges the thickness of section 32 and reduces gradually from bottom to top. The first avoiding section 31 is arranged at the bottom end of the heating plate 3, so that the fluidized carbon-based material moves upwards smoothly and smoothly enters the region coated by the heating plate 3, and the deposition effect is improved. Set up the second on the top of hot plate 3 and dodge the end, make the downward motion of deposit material smooth and easy, can avoid deposit material at the top of hot plate 3 deposit.
In this embodiment, the fluidization chamber 11 includes a straight cylinder section and an expanding section 21 connected to the upper end of the straight cylinder section, the inner diameter of the expanding section 21 gradually increases from bottom to top, a splitter plate 10 is disposed in the expanding section 21, the filtering splitter plate 10 is a conical filter plate with an upward vertex, the negative pressure recovery assembly 9 is communicated with the space above the splitter plate 10, and the carbon-based material conveying mechanism 4 and the gas-phase material conveying mechanism 5 are both communicated with the straight cylinder section. The fluidized deposition material in the fluidizing chamber 11 is in a suspension state, so that the flow guide is formed, and the deposition effect is improved.
In this embodiment, the collecting hopper 7 includes a collecting chamber 71 and a discharge port 72 communicating with the collecting chamber 71, the collecting chamber 71 has a guide inclined surface 711 for guiding the fluidized deposition material in the collecting chamber 71 to the discharge port 72, and the discharge port 72 is provided with a valve 73 for opening and closing the discharge port 72. When the valve 73 closes the discharge port 72, the fluidized deposition material is collected in the accumulation chamber 71; when the valve 73 is opened, the fluidized deposition material in the collecting chamber 71 is discharged from the discharge hole 72, and the guide inclined surface 711 of the collecting chamber 71 makes the fluidized deposition material in the collecting chamber 71 flow toward the discharge hole 72, so that the fluidized deposition material in the collecting chamber 71 can be smoothly discharged outward.
In this embodiment, a condenser and a cyclone are provided at the discharge port 72 of the collection hopper 7. The condenser is used for condensing and recovering the silicon source gas, the reducing gas, and the carrier gas discharged from the discharge port 72. The cyclone is used to recover the unreacted carbon-based material discharged from the discharge port 72. The material is recovered through the condenser and the cyclone separator, so that the material utilization rate is improved, the cost is reduced, and the environment friendliness is good.
In this embodiment, the carbon-based material conveying mechanism 4 is a screw feeder, a peristaltic pump, or a pneumatic conveyor. The carbon-based material conveying mechanism 4 works reliably and can stably and uniformly convey the carbon-based material in the phase reaction cavity 1.
In this embodiment, the gas-phase material conveying mechanism 5 and the carrier gas conveying mechanism 6 are both gas tanks.
In this embodiment, the heating device adopts modes such as electric heating, microwave heating or high temperature flue gas to heat.
In this embodiment, the negative pressure recovery assembly 9 is a high-temperature vacuum pump, and the high-temperature vacuum pump is used for recovering unreacted carbon-based materials.
Example 2:
the preparation method of the silicon-carbon negative electrode material of the embodiment, which is performed by using the CVD fluidized deposition apparatus of the embodiment 1, includes the following steps:
s1: the carrier gas N is input into the reaction chamber 1 through the carrier gas conveying mechanism 62Gas flow of 2Nm3H, enabling the pressure in the reaction cavity 1 to reach 1bar, inputting 1kg of artificial graphite with the median particle size of 3um into the reaction cavity 1 through a screw feeder, and adjusting the guide plate 8 to enable the artificial graphite to generate fluidization;
s2: starting a heating device to heat the reaction cavity 1, so that the temperature in the reaction cavity 1 is raised to 800 ℃;
s3: h with a molar ratio of 5:1 is fed by a gas-phase material feeding mechanism 52And SiH4Introducing into the reaction chamber 1 SiH4Carrying out CVD fluidized deposition with artificial graphite in the reaction chamber 1 to form a fluidized deposition material;
s4: after 2h, the SiH input into the reaction chamber 1 is stopped4Opening the negative pressure recovery component 9 to extract unreacted artificial graphite, and continuously inputting carrier gas N2Until the temperature of the reaction cavity 1 is reduced to room temperature;
s5: the silicon carbon anode material is collected from the collection hopper 7.
Example 3:
the preparation method of the silicon-carbon negative electrode material of the embodiment, which is performed by using the CVD fluidized deposition apparatus of the embodiment 1, includes the following steps:
s1: inputting carrier gas Ar into the reaction cavity 1 through a carrier gas conveying mechanism 6 to enable the pressure in the reaction cavity 1 to reach 0.5bar, conveying 5kg of graphene oxide dispersion liquid with the solid content of 1% and the median particle size of 5 microns into the reaction cavity 1 through a peristaltic pump in a spraying mode, and adjusting a guide plate 8 to enable the artificial graphite to be fluidized;
s2: starting a heating device to heat the reaction cavity 1, so that the temperature in the reaction cavity 1 is raised to 200 ℃;
s3: h is fed by the gas-phase material feeding mechanism 52、SiHCl3And SiBr4Conveying the mixture into a reaction cavity 1 according to a molar ratio of 10:1:1 to ensure that SiHCl is delivered3And SiBr4Carrying out CVD fluidized deposition with graphene oxide in the reaction chamber 1 to form a fluidized deposition material;
s4: after 10h, the SiHCl input into the reaction chamber 1 is stopped3And SiBr4Starting the negative pressure recovery assembly 9 to extract unreacted artificial graphite, and continuously inputting carrier gas Ar until the temperature of the reaction cavity 1 is reduced to room temperature;
s5: the silicon carbon anode material is collected from the collection hopper 7.
The SEM image of the obtained silicon carbon negative electrode material is shown in fig. 2.
Example 4:
the preparation method of the silicon-carbon negative electrode material of the embodiment, which is performed by using the CVD fluidized deposition apparatus of the embodiment 1, includes the following steps:
s1: the carrier gas N is input into the reaction chamber 1 through the carrier gas conveying mechanism 62The pressure in the reaction cavity 1 reaches 100bar, 1kg of natural graphite with the median particle size of 5um is conveyed into the reaction cavity 1 through a pneumatic conveyor, and the flow guide plate 8 is adjusted to fluidize the artificial graphite;
s2: starting a heating device to heat the reaction cavity 1, so that the temperature in the reaction cavity 1 rises to 1200 ℃;
s3: h is fed by the gas-phase material feeding mechanism 52、SiH2Cl2And SiH4The mixture is conveyed into a reaction chamber 1 according to the molar ratio of 20:1:1 to cause SiH2Cl2And SiH4Carrying out CVD fluidized deposition with natural graphite in the reaction chamber 1 to form a fluidized deposition material;
s4: after 5h, SiH input into the reaction chamber 1 is stopped2Cl2And SiH4Opening the negative pressure recovery component 9 to extract unreacted natural graphite, and continuously inputting carrier gas N2Until the temperature of the reaction cavity 1 is reduced to room temperature;
s5: the silicon carbon anode material is collected from the collection hopper 7.
Comparative example 1:
commercial nano silicon with the median particle size of 30nm and natural graphite with the median particle size of 5um are mixed and uniformly mixed through a VC (vinyl chloride) mixer to prepare the silicon-carbon negative electrode material.
Comparative example 2:
the nano silicon with the median particle size of 100nm is prepared by adopting a mechanical grinding mode, and is mixed with natural graphite with the median particle size of 5um to prepare the silicon-carbon negative electrode material by adopting modes of binder mixing, spraying, compression molding, liquid phase coating granulation and the like.
The above examples 2 to 4 and comparative examples 1 to 2 were characterized and tested by the following methods:
testing the particle size distribution condition of the silicon-carbon negative electrode material by using a Malvern laser particle size tester MS 2000;
observing the surface appearance, the particle size and the like of a sample by adopting a field emission scanning electron microscope;
testing a silicon crystal structure in the silicon-carbon negative electrode material by using an X-ray diffractometer (testing equipment);
the electrochemistry was tested using the following method: pulping the silicon-carbon negative electrode material, the conductive agent and the binder according to the mass ratio of 94:1:5, controlling the solid content of the slurry to be about 40%, and coating the slurry on a copper foil current collector to obtain a negative electrode plate; using a metallic lithium plate as a counter electrode, 1mol/L LiPF6And the/EC + DMC electrolyte is assembled into a 2032 button cell. The battery adopts an LAND battery test system, and is tested under the condition of constant current charge and discharge at 0.1 ℃, and the voltage range is 0.005-1.5V;
the results of the battery tests performed on the examples and comparative examples, respectively, are shown in the following table:
the table shows that the silicon-carbon cathode material prepared by the CVD fluidized deposition device can be directly applied to batteries. The performance of the silicon-carbon cathode material prepared by the equipment is closer to the capacity and the first effect of the silicon-carbon cathode material prepared by the grinding process in the current market, and the cycle performance is better. The problems of complex process, small mechanical grinding capacity and the like exist in the prior physical grinding preparation of nano silicon-carbon materials; the method has simple equipment and simple process, and can provide certain reference significance for large-scale production of the silicon-carbon cathode.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (10)
1. A CVD fluidization deposition device comprises a fluidized bed (2) with a reaction cavity (1), wherein a heating device for heating the reaction cavity (1) and a collection hopper (7) for collecting fluidization deposition materials are arranged in the reaction cavity (1), the CVD fluidization deposition device is characterized in that the fluidized bed (2) is connected with a carbon-based material conveying mechanism (4) for conveying carbon-based materials into the reaction cavity (1), a gas-phase material conveying mechanism (5) for conveying silicon source gas and reducing gas into the reaction cavity (1), a carrier gas conveying mechanism (6) for inputting carrier gas into the reaction cavity (1) and a negative pressure recovery assembly (9) for recovering excess materials, a guide plate (8) for dividing the reaction cavity (1) into a fluidization cavity (11) and a discharge cavity (12) is arranged in the reaction cavity (1), the carbon-based material conveying mechanism (4), the gas-phase material conveying mechanism (5) and the negative pressure recovery assembly (9) are all communicated with the fluidization cavity (11), the carrier gas conveying mechanism (6) is communicated with the discharging cavity (12).
2. The CVD fluidized deposition device according to claim 1, wherein the fluidizing chamber (11) comprises a straight cylinder section and an expanding section (21) connected to the upper end of the straight cylinder section, the inner diameter of the expanding section (21) is gradually increased from bottom to top, a splitter plate (10) is arranged in the expanding section (21), the filtering splitter plate (10) is a conical filter plate with an upward vertex, the negative pressure recovery assembly (9) is communicated with a space above the splitter plate (10), and the carbon-based material conveying mechanism (4) and the gas-phase material conveying mechanism (5) are both communicated with the straight cylinder section.
3. A CVD fluidized deposition apparatus according to claim 1, wherein the collection hopper (7) comprises a collection chamber (71) and a discharge port (72) communicating with the collection chamber (71), the collection chamber (71) has a guide inclined surface (711) for guiding the fluidized deposition material in the collection chamber (71) to the discharge port (72), and the discharge port (72) is provided with a valve (73) for opening and closing the discharge port (72).
4. A CVD fluidized deposition apparatus according to claim 3, characterized in that the discharge opening (72) of the collecting hopper (7) is provided with a condenser and a cyclone.
5. The CVD fluidization deposition device according to claim 1, wherein the heating device comprises a cylindrical heating plate (3) installed in a fluidization chamber (11), the cylindrical heating plate (3) is attached to the inner side wall of the circular reaction chamber (1), a first avoidance section (31) is arranged at the bottom end of the cylindrical heating plate (3), the thickness of the first avoidance section (31) is gradually reduced from top to bottom, a second avoidance section (32) is arranged at the top end of the cylindrical heating plate (3), and the thickness of the second avoidance section (32) is gradually reduced from bottom to top.
6. A preparation method for preparing a silicon-carbon negative electrode material by using the CVD fluidized deposition device of any one of claims 1 to 5, which is characterized by comprising the following steps:
s1: inputting carrier gas into the reaction cavity (1) through the carrier gas conveying mechanism (6) to enable the pressure in the reaction cavity (1) to reach a preset pressure, inputting the carbon-based material into the reaction cavity (1) through the carbon-based material conveying mechanism (4), and adjusting the guide plate (8) to enable the carbon-based material to generate fluidization;
s2: starting a heating device to heat the reaction cavity (1) so as to raise the temperature in the reaction cavity (1) to a preset reaction temperature;
s3: silicon source gas and reducing gas in a preset proportion are input into the reaction chamber (1) through the gas-phase material conveying mechanism (5), so that the silicon source gas and the carbon-based material are subjected to CVD fluidized deposition in the reaction chamber (1) to form a fluidized deposition material;
s4: stopping inputting silicon source gas into the reaction chamber (1) after preset time, starting the negative pressure recovery assembly (9) to extract unreacted carbon-based materials, and continuously inputting carrier gas until the temperature of the reaction chamber (1) is reduced to room temperature;
s5: and collecting the silicon-carbon negative electrode material from a collecting hopper (7).
7. The method for preparing the silicon-carbon anode material of claim 6, wherein the silicon source gas is one or a combination of more than two of silane, disilane, dichlorosilane, trichlorosilane, tetrachlorosilane, dibromosilane, tribromosilane and tetrabromosilane.
8. The method as claimed in claim 6, wherein the predetermined reaction temperature is 500-1500 ℃.
9. The method for preparing a silicon-carbon anode material according to claim 6, wherein the preset pressure is 0.01-100 bar.
10. The method for preparing a silicon-carbon anode material according to claim 6, wherein the reducing gas is hydrogen, and the predetermined ratio is the reducing gas in terms of molar ratio: 1 is silicon source gas (2-10); or the reducing gas is nitrogen, and the preset proportion is that the reducing gas is calculated according to the molar ratio: and (1-20) the silicon source gas is 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111070124.3A CN113957417A (en) | 2021-09-13 | 2021-09-13 | CVD fluidized deposition device and preparation method of silicon-carbon negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111070124.3A CN113957417A (en) | 2021-09-13 | 2021-09-13 | CVD fluidized deposition device and preparation method of silicon-carbon negative electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113957417A true CN113957417A (en) | 2022-01-21 |
Family
ID=79461444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111070124.3A Pending CN113957417A (en) | 2021-09-13 | 2021-09-13 | CVD fluidized deposition device and preparation method of silicon-carbon negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113957417A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110220024A1 (en) * | 2008-10-09 | 2011-09-15 | Comm. A L'energie Atomique Et Aux Energies Alter. | Device for the synthesis of nanoparticles by fluidized-bed chemical vapour deposition |
| US20120148728A1 (en) * | 2010-12-09 | 2012-06-14 | Siliken Sa | Methods and apparatus for the production of high purity silicon |
| CN103172067A (en) * | 2013-04-08 | 2013-06-26 | 无锡中彩科技有限公司 | Cold wall fluidized bed and application thereof |
| CN107708852A (en) * | 2015-04-12 | 2018-02-16 | 加州锂电池公司 | Equipment and technique for semicontinuous and multistep processes production composite |
| CN111188022A (en) * | 2020-02-25 | 2020-05-22 | 上海旦元新材料科技有限公司 | Preparation method of silicon cathode material coated by vapor deposition carbon nanotube |
| CN113215552A (en) * | 2021-04-23 | 2021-08-06 | 株洲弗拉德科技有限公司 | Method for preparing coating powder by adopting plasma vapor deposition process |
-
2021
- 2021-09-13 CN CN202111070124.3A patent/CN113957417A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110220024A1 (en) * | 2008-10-09 | 2011-09-15 | Comm. A L'energie Atomique Et Aux Energies Alter. | Device for the synthesis of nanoparticles by fluidized-bed chemical vapour deposition |
| US20120148728A1 (en) * | 2010-12-09 | 2012-06-14 | Siliken Sa | Methods and apparatus for the production of high purity silicon |
| CN103172067A (en) * | 2013-04-08 | 2013-06-26 | 无锡中彩科技有限公司 | Cold wall fluidized bed and application thereof |
| CN107708852A (en) * | 2015-04-12 | 2018-02-16 | 加州锂电池公司 | Equipment and technique for semicontinuous and multistep processes production composite |
| CN111188022A (en) * | 2020-02-25 | 2020-05-22 | 上海旦元新材料科技有限公司 | Preparation method of silicon cathode material coated by vapor deposition carbon nanotube |
| CN113215552A (en) * | 2021-04-23 | 2021-08-06 | 株洲弗拉德科技有限公司 | Method for preparing coating powder by adopting plasma vapor deposition process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109119627A (en) | A kind of preparation method and device of high performance silicon carbon based negative electrodes material | |
| US20150099174A1 (en) | Silicon Monoxide Composite Negative Electrode Material used for Lithium Ion Battery, the Preparation Method Thereof and a Lithium Ion Battery | |
| CN102427130A (en) | Lithium iron phosphate-carbon nanotube composite material, preparation method, and application thereof | |
| CN102593446A (en) | Method for preparing active electrode material of lithium ion battery | |
| CN107026258A (en) | SiO/C combination electrode materials of conductive support load and its preparation method and application | |
| CN110729471B (en) | Silicon @ graphene/CVD carbon composite anode material for lithium ion battery and preparation method and application thereof | |
| CN111668474A (en) | Negative electrode material, preparation method thereof and secondary battery | |
| CN110890537B (en) | Production method of high-purity nanocrystalline silicon | |
| CN106252622B (en) | A kind of silica/carbon composite nano line negative electrode material, preparation method and lithium ion battery | |
| CN107195903A (en) | A kind of lithium-ion-power cell small particle natural graphite negative electrode material and preparation method thereof | |
| CN112271298A (en) | High-capacity nitrogen-doped carbon-coated SnOxPreparation method of quantum dot lithium ion battery cathode material | |
| CN113380997B (en) | Silicon-based negative electrode material of lithium ion battery and preparation method thereof | |
| CN112768667A (en) | Lithium ion battery silicon-carbon negative electrode material and preparation process and equipment thereof | |
| CN114314564A (en) | Carbon nanotube conductive network coated SiO @ C composite material and preparation method and application thereof | |
| CN113957417A (en) | CVD fluidized deposition device and preparation method of silicon-carbon negative electrode material | |
| CN112028075A (en) | Preparation method of nano SiC used as lithium ion battery cathode material | |
| CN113471440B (en) | Silica material, preparation method and application thereof | |
| CN112768666A (en) | Lithium ion battery silicon-carbon negative electrode material and preparation process and equipment thereof | |
| CN115172723A (en) | Preparation process of silicon-carbon composite material for lithium ion battery | |
| CN112768668A (en) | Lithium ion battery silicon-carbon negative electrode material and preparation process and equipment thereof | |
| CN109301268A (en) | Li-CO2Anode catalyst material and preparation method thereof, cell positive material and battery | |
| CN114401926A (en) | Continuous preparation method and production equipment of spherical negative electrode active material | |
| CN109638266B (en) | Carbon-coated selenium indium lithium material and preparation method and application thereof | |
| CN110537272B (en) | Silicon powder especially suitable for anode of lithium ion battery and its production method and use | |
| CN109449416B (en) | Silica material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |